Process for electrolysis of sodium chloride

ABSTRACT

A process for the electrolysis of aqueous solutions of sodium chloride in an electrolytic cell separated into an anode chamber and a cathode chamber by a cation exchange membrane consisting essentially of perfluorocarbon polymer having pendant carboxylic acid and sulfonic acid groups, said membrane having an ion exchange capacity of sulfonic and carboxylic acid groups of from 0.5 to 4.0 milliequivalents per gram of dry resin, the ion exchange capacity of the carboxylic acid groups being from 0.05 to 1.5 milliequivalents per gram of dry resin.

RELATED APPLICATIONS

This application is a divisional of copending application Ser. No.836,417, filed on Sept. 26, 1977, now abandoned, which is acontinuation-in-part of application Ser. No. 745,196, filed on Nov. 26,1976, now abandoned, which is, in turn, a continuation of applicationSer. No. 556,288, filed on Mar. 7, 1975, now abandoned. Application Ser.No. 959,312, a divisional of said application Ser. No. 836,417, issuedas U.S. Pat. No. 4,178,218 on Dec. 11, 1979. This case is also relatedto application Ser. No. 214,876, filed on Dec. 10, 1980, (now U.S. Pat.No. 4,357,218) a divisional of Ser. No. 836,417.

BACKGROUND OF THE INVENTION

A large proportion of chlorine and caustic produced throughout the worldis manufactured in diaphragm type electrolytic cells wherein the opposedanode and cathode are separated by a fluid permeable diaphragm which maybe of asbestos, a polymer film or a polymer film supported on asbestos.The diaphragm defines separate anolyte and catholyte compartments.Chlorine is produced in the former, aqueous sodium hydroxide in thelatter.

In operation, brine, preferably saturated, is fed to the anolytecompartment. The brine passes through the diaphragm into the catholytecompartment where an aqueous sodium hydroxide solution of about 11 to 18percent is produced. This solution is contaminated by sodium chloridewhich must be separated. After separation, the caustic solution isconcentrated to produce the commercial product.

The permionic exchange membrane type electrolytic cell has been utilizedas an improvement over the diaphragm type. The permionic membranereplaces the diaphragm, and is characteristically different from itsince, in contrast to the diaphragm, it is substantially impervious towater and to sodium chloride. The exchange membrane selected for theproduction of chlorine and caustic is usually a cation exchange membranewhich permits the passage of sodium ions into the catholyte, butprevents back-migration of OH ions into the anolyte. As a result,relatively pure caustic substantially free of sodium chloride isproduced in the catholyte, and high grade chlorine is produced at theanode.

A number of cation exchange membranes are known.

U.S. Pat. Nos. 3,887,499 and 3,657,104 describe permselective cationexchange membranes comprising a hydrocarbon polymer backbone withpendant carboxylic and sulfonic groups.

U.S. Pat. No. 3,878,072 describes cation exchange membranes which arehydrolyzed copolymers of a perfluorinated hydrocarbon and either afluorosulfonated perfluorovinyl ether or a sulfostyrenatedperfluorinated ethylene propylene polymer. In either event, thecharacteristic feature of the membrane is the sulfonyl group as the onlyfunctional group.

U.S. Pat. No. 3,853,721 which issued on Dec. 10, 1974 describes asbestosdiaphragms containing from about 0.01 to 22 weight percent, based on theweight of the diaphragm, of an ion exchange resin which is afluorocarbon polymer characterized by the presence of the followinggroups:

sulfonic--SO₃ H

fluoromethylene sulfonic--CF₂ SO₃ H

benzene sulfonic--φSO₃ H

chloromethylene sulfonic--CCl₂ SO₃ H

carboxylic--COOH

phosphoric--PO₃ H₂

phosphorous--PO₂ H₂

phenolic--φOH

A characteristic feature of these diaphragms is that they are gas andelectrolyte permeable in contrast to permionic membranes, such as thecationic ion exchange membranes of this invention which aresubstantially impermeable to electrolytes, but permit the passage ofions. Another feature, according to the patent, is that they have aresistance voltage drop across the diaphragm of as much as 0.2 to 0.3volt less than an untreated asbestos diaphragm of the same thickness.

A problem with the use of diaphragm electrolysis, as pointed out above,is that the permeability of the diaphragm to sodium chloride results inaccumulation of this material in the catholyte. This concentration maybe as high as 17%. When attempts are made to produce concentratedsolutions of sodium hydroxide in the catholyte by evaporation of water,it is necessary to use an expensive apparatus as well as a large amountof energy.

U.S. Pat. No. 3,301,893 discloses certain fluorocarbon ethers containingboth carboxyl and sulfonyl groups. The products of this patent, however,are of such low molecular weight that they cannot be utilized for thepreparation of cation exchange membranes.

THE INVENTION

It has now been discovered that many of the difficulties of the priorart can be minimized or completely avoided by the utilization ofpermselective cationic ion exchange membranes in which carboxylic acidgroups or both carboxylic and sulfonic acid groups are pendant from afluorocarbon polymer.

Membranes of this type manifest a number of significant advantages.Those characterized by the presence of carboxyl groups manifest:

1. Decreased back-migration of hydroxyl ions.

2. Increased current efficiency at high current density even when theconcentration of sodium hydroxide in the catholyte is high.

3. Increased purity of the sodium hydroxide solution produced in thecathode because of the resistance of the membrane to permeation bysodium chloride.

4. Increased purity of chlorine produced at the anode.

5. Resistance to oxidation.

Those membranes which have both carboxylic and sulfonic groups are muchpreferred embodiments of this invention. They exhibit all of the aboveadvantages and, in addition:

1. Their useful life in operation is surprisingly long.

2. Power consumption in units in which they are employed is surprisinglylow.

The membranes of this invention are prepared from fluorocarbon polymerswith pendant carboxylic acid groups, or pendant carboxylic acid andsulfonic acid groups. The pendant groups may be chemically bonded to thefluorocarbon polymer. Alternatively, they may become integral with thepolymer by impregnation and coating techniques followed bypolymerization as described more fully hereinafter. Since membranesprepared by both procedures are functional equivalents, they will bedescribed in the specification and claims as fluorocarbon polymermembranes having pendant carboxyl groups, or pendant carboxyl andsulfonic groups. Often the polymers will be crosslinked to increaseresistance to solvent and temperature under electrolysis conditions.Many linear polymers, however, are completely satisfactory. For example,a crosslinking agent such as divinyl benzene may be added to a monomermixture used to impregnate or coat a fluorocarbon membrane. Uponcompletion of polymerization, the dimensional stability of the membranemay be greatly improved.

As mentioned above, the carboxylic acid groups may be bonded chemicallyto the fluorocarbon polymer. Alternatively, a polymer having carboxylicacid groups may be combined physically with the fluorocarbon polymer. Inthe latter case, the polymer having carboxylic acid groups may bedispersed uniformly throughout the fluorocarbon matrix or it may bepresent in layers on the fluorocarbon polymer. Such products may beprepared by coating or impregnating a fluorocarbon polymer membranewhich may or may not have sulfonic acid groups with a carboxylic acidgroup-containing monomer and, thereafter, effecting polymerization.

As mentioned above, when both sulfonic acid and carboxylic acid groupsare present on the membrane, it will have high electric conductivity,with a resulting decrease in power cost and increasing commercialadvantages. The advantages are especially apparent when the ratio ofcarboxylic acid groups to sulfonic acid groups is from 1:100 to 100:1.

When practicing this invention, the acid groups may be either in theform of free acid or metal salts.

The cation exchange membrane of this invention wherein the acid groupsare directly attached to the base fluorocarbon polymer may be preparedas follows:

1. A membrane made from a polymer produced by polymerizing a vinyl etherof the general formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

(wherein n is an integer of 2 to 12, preferably 2 to 4; and X is --CN,--COF, --COOH, --COOR, --COOM or --CONR₂ R₃, where R is an alkyl groupcontaining 1 to 10, preferably 1 to 3, carbon atoms; R₂ and R₃ areindividually hydrogen or one of the groups represented by R; and M issodium, potassium or cesium) with tetrafluoroethylene and/or CF₂═CF--O--R_(f) (wherein R_(f) is a perfluorinated alkyl group containing1 to 3 carbon atoms), and hydrolyzing the polymer where necessary toform acid groups;

2. A polymer membrane made by polymerizing a perfluoroacrylic monomerrepresented by the general formula:

    CF.sub.2 ═CFCOZ

(wherein Z is fluorine or an alkoxy group containing 1 to 10, preferably1 to 3 carbon atoms, amino or a hydroxy group) with tetrafluoroethyleneand CF₂ ═CF--O--R_(f) and hydrolyzing where necessary to form acidgroups; and

3. a membrane made by polymerizing a perfluorocarbon vinyl ether of thegeneral formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X,

a perfluorocarbon sulfonyl fluoride of the general formula:

    FSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m CF═CF.sub.2

(wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3) with tetrafluoroethylene and/or CF₂ ═CF--O--R_(f),and hydrolyzing where necessary to form acid groups.

Cation exchange membranes of the invention in which the pendant acidgroups are physically combined with the base are prepared as follows:

4. A membrane of fluorocarbon polymer, e.g. a homo-or copolymer of suchmonomers as tetrafluoroethylene, hexafluoropropylene or perfluoromethylperfluorovinyl ether is coated or impregnated with CF₂ ═CF--O--(CF₂)_(n)--X, wherein X has the same meaning as in (1) above, polymerizing and,if necessary, hydrolyzing to form the acid;

5. A copolymer membrane made from a perfluorovinyl ether derived monomerwhich has an LSO₂ group convertible to sulfonic acid of the generalformula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m CF═CF.sub.2

(wherein L is OH, fluorine or OA, where A is a quaternary ammoniumradical), tetrafluoroethylene and CF₂ ═CF--O--R_(f) is impregnated orcoated with CF₂ ═CF--O--(CF₂)_(n) --X, followed by polymerization, and,if necessary, hydrolysis to form the acid;

6. A membrane made from a perfluorovinyl ether derived monomer having agroup convertible to a sulfonic acid group and having the generalformula LSO₂ CFR_(g) CF₂ O(CFYCF₂ O)_(m) CF═CF₂, as in (5) above, isimpregnated or coated with perfluoroacrylic acid or perfluorocarbonylfluoride, followed by polymerization, and, if necessary, hydrolysis toform the acid;

7. A fluorocarbon polymer membrane having no ion exchange group isimpregnated or coated with a vinyl compound having a COOR group, whereinR is alkyl containing from 1 to 10 carbon atoms, followed bypolymerization, and, if necessary, hydrolysis to form the acid; and

8. A membrane made from a perfluorovinyl ether derived monomer of thegeneral formula LSO₂ CFR_(g) CF₂ O(CFYCF₂ O)_(m) CF═CF₂ as in (5) above,is impregnated or coated with a vinyl compound having a COOR group, asin (7) above, followed by polymerization, and, if necessary, hydrolysisto form the acid.

Among the polymers mentioned in the above, copolymers comprising CF₂═CF--OR_(f) and CF₂ ═CF--O--(CF₂)_(n) --X or CF₂ ═CF--COZ and thecopolymer comprising CF₂ ═CF--OR_(f), CF₂ ═CF₂ and CF₂ ═CF--O--(CF₂)_(n)--X or CF₂ ═CF--COZ are preferred because of the ease with which theycan be formed into membranes.

When the monomers are impregnated into or coated on the polymer in thepreparation of the above membranes, the polymerization may be effectedin the presence of a crosslinking agent or a solvent, if desired.

Typical examples of the fluorinated perfluorovinyl ether of the generalformula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

are methyl perfluoro-6-oxa-7-octenoate, methylperfluoro-5-oxa-6-heptenoate, perfluoro-6-oxa-7-octenoyl fluoride andperfluoro-6-oxa-7-octenenitrile.

Typical examples of an LSO₂ group containing perfluorovinyl etherderivative of the general formula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m CF═CF.sub.2

are the triethylammonium salts ofperfluoro[2-(2-fluorosulfonylethoxy)-propylvinyl ether] such as (C₂ H₅)₃HN--O--SO₂ CF₂ CF₂ OCF(CF₃)--CF₂ OCF═CF₂.

Typical examples of the vinyl ether of the general formula:

    CF.sub.2 ═CFOR.sub.f

are perfluoromethyl perfluorovinyl ethers.

Typical examples of the perfluorocarbon polymer free from COOR groupsare homopolymers of tetrafluoroethylene, hexafluoropropene, vinylidenefluoride, perfluoromethyl perfluorovinyl ether, chlorotrifluoroethylene,1,1,3,3,3-pentafluoropropene and 1,2,3,3,3-pentafluoropropene,alternating copolymers of these monomers and copolymers of thesemonomers with ethylene.

As crosslinking agents, there may be used fluorinated diolefins of thegeneral formula:

    CF.sub.2 ═CF--O--(CF.sub.2 CF.sub.2 --O).sub.n CF═CF.sub.2,

in addition to such diolefin compounds as, for example, divinylbenzeneand butadiene. When a membrane made from a fluorocarbon polymer withpendant sulfonic groups is coated or impregnated with a monomer such asacrylic acid and polymerized in the presence of divinylbenzene, theresulting cation exchange membrane is greatly improved in dimensionalstability.

As is clear from the above explanation, the cation exchange membranes ofthis invention can be prepared by a variety of methods utilizing manydifferent monomers. They may be homopolymers or copolymers, includingmore than two monomeric units. As is standard in the art, fluorocarbonrefers to fluorine containing monomers which may contain hydrogen,chlorine or other atoms attached to carbon atoms, e.g.chlorotrifluoroethylene and vinylidene fluoride. Perfluorocarbons aremonomers in which the hydrogens are all replaced with fluorine. Forstability, the latter are preferred.

Standard polymerization procedures including solution, emulsion andsuspension polymerization may be employed. Polymerization may beinitiated by free radical mechanisms or other procedures. The resultingpolymer is molded into a membrane according to an ordinary moldingprocedure such as melt fabrication or the like. The cation exchangemembranes may often be prepared directly by casting polymerizationtechniques. When a fluorocarbon polymer having ion exchange groups isimpregnated or coated with acrylic acid or the like monomer havingcarboxylic groups, and, if desired, with a crosslinking agent and thenpolymerized, the polymerization may be in the presence of a free radicalpolymerization catalyst such as a peroxide, by the action of high energyionizing radiation, or by other means.

Generally, the cation exchange membranes used in this invention willhave an exchange capacity, in terms of carboxylic acid groups, of 0.1 to10 milliequivalents, preferably 0.5 to 4.0 milliequivalents, per gram ofdry resin. When sulfonic acid groups are also present in the membranes,the exchange capacity of the sulfonic acid groups is 0.1 to 10milliequivalents, preferably 0.5 to 4.0 milliequivalents, per gram ofdry resin.

The cation exchange membrane used in the present invention may sometimesbe reinforced in mechanical strength by incorporating into the membranea net of fibers of other fluorocarbon polymer. For industrial purposes,the use of a cation exchange membrane, which has been linked with Teflonfibers, is preferable, in general. The thickness of the membrane is 0.01to 1.5 mm, preferably 0.05 to 1.5 mm, and may be suitably selected sothat the specific conductivity and current efficiency of the membrane issuch that it may be successfully employed in the electrolysis of sodiumchloride in the selected electrolytic cell.

The cation exchange membrane of this invention contain 5 to 50%, basedon their own weight, of water in the sodium salt form membrane. Themembranes are utilized to divide the electrolytic cell employed into acathode chamber and an anode chamber. Electrolysis is performed bycharging the anode chamber with an aqueous sodium chloride solution,while adding to the cathode chamber water, or a dilute sodium hydroxidesolution, which may be recycled to control the concentration of sodiumhydroxide at the outlet of the cathode chamber. The concentration of thesodium chloride solution charged to the anode chamber is normally high,preferably near saturation.

The electrolysis may be effected at a temperature of 0° to 150° C., andheat generated due to the electrolysis is removed by cooling a part ofthe anolyte or catholyte.

In the cathode and anode chambers, there are generated hydrogen andchlorine, respectively. To prevent the membrane from contacting eitherelectrode, a spacer may be interposed between the two. The separation ofthe gases from the liquids is desirably conducted by providing a freespace at the upper portion of each chamber of the electrolytic cell. Inthis case, it is sometimes desirable that the gases and the effluents bedischarged separately, though discharging them together may be effectedin the cathode or anode chambers. When separation of gas from liquid iseffected in the upper free space within the electrolytic cell, therecycle of the electrolyte in each chamber can advantageously bepromoted by the ascending action of the formed gases, in general. Thisis particularly apparent where the electrolytic cell has been sodesigned that the formed gases are introduced at the back side of eachelectrode and are ascending so that the space between the electrode andthe membrane surface is gas free. Amongst the advantages of this designare decreased potential depression and lower power consumption.

The perpass electrolysis ratio of sodium chloride charged to the anodechamber may be 3 to 50%. This varies depending on the current densityand the manner of heat removal, but is normally maintained as high aspossible.

The liquid in each chamber is desirably stirred by means of the gasesgenerated in the cathode and anode chambers, in addition to the flow ofexternally supplied fluids. For this purpose also, it is desirable thatan electrode having many vacant spaces such as a metal mesh electrode isused so that the liquid in each chamber can be moved, circulated andstirred with ascending flow of the gases.

As the cathode, the use of an iron electrode which has been plated withnickel or a nickel compound is preferable, in general, from thestandpoint of overpotential. As the anode, the use of a metal mesh orrod electrode which has been coated with an oxide of a noble metal suchas ruthenium or the like is preferred. Use of these types of electrodesmakes it possible to minimize the interval between membranes andelectrodes so that power consumption and potential depression duringelectrolysis are minimized. By the use of the membranes, back-migrationof OH ions is inhibited and the cathode and anode chambers aredistinctly separated from each other. Accordingly, when metal electrodeshigh in mechanical dimensional precision are used in combination withthe cation exchange membrane of this invention, the interval betweeneach electrode and the membrane can be made extremely small, e.g. about1 to 3 mm, so that electrolysis can be effected at a high currentdensity while minimizing the potential depression and while maintaininglow power consumption. These characteristics are not observed in theconventional diaphragm process.

Cation exchange membranes of this invention are resistant to chlorinegenerated in the anode chamber, so that the electrolysis operation canbe carried out stably over a long period of time. Additionally, asindicated above, back-migration of hydroxyl ions is inhibited. As aresult, the pH of the liquid in the anode chamber can be easilymaintained at from neutral to slightly acidic, and thus the content ofoxygen in the chlorine generated in the anode chamber can be maintainedas low as less than 500 p.p.m.

By utilizing the cation exchange membranes of the invention, currentefficiency is far higher than can be achieved with cation exchangemembranes prepared from perfluorocarbon polymers with sulfonic acidgroups as the only ion exchange groups. The production, in the cathodechamber, of sodium hydroxide at a concentration of more than 20% can beeffected with a current efficiency of at least 80%, and about 90 to 98%under optimum conditions. Since the current efficiency is high and thepower consumption low, cells using membranes of this invention can beoperated economically at current densities as high as 20 to 70 A/dm². Aprincipal reason contributing to the high current efficiency is theinhibition of back-migration of OH ions.

The aqueous sodium chloride solution charged to the anode chamber ispurified, as in conventional sodium chloride electrolysis processes. Itmay be subjected to the dechlorination, dissolution and saturation ofsodium chloride, precipitation and separation of magnesium, calcium,iron, etc., and neutralization, as in other procedures. It may also bedesirable to further purify the feed sodium chloride solution with agranular ion exchange resin, particularly a chelate resin, to reduce thecalcium content thereof to an acceptable limit, preferably to less than1 p.p.m.

While this invention should not be limited by theory, it appearspossible that the advantages of this invention are attained because ofthe low dissociation constant of carboxylic acid groups. As a result ofthe low dissociation constant, the carboxyl groups in the membrane incontact with the anolyte having a high hydrogen ion concentration existin the hydrogen form, which makes the membrane structure more compactand effectively inhibits the back-migration of hydroxyl ions. Thiseffect cannot be achieved with membranes in which the only pendantgroups are sulfonic acid groups.

The following non-limiting examples are given by way of illustrationonly.

EXAMPLE 1

A copolymer of perfluoro[2-(2-fluorosulfonylethoxy)propylvinyl ether]with tetrafluoroethylene is molded into a membrane 0.12 mm in thickness,which is then hydrolyzed to prepare a cation exchange membrane having anexchange capacity, in terms of sulfonic acid groups, of 0.88milliequivalent per gram of dry resin.

This perfluorosulfonic acid type cation exchange membrane is impregnatedwith a solution of perfluoroacrylic acid, and the latter is thenpolymerized to obtain a perfluorovinyl ether type cation exchangemembrane, in which the perfluoroacrylic acid polymer is present inadmixture with the perfluorosulfonic acid type polymer.

The cation exchange membrane contains 0.75 milliequivalent per gram ofdry resin of sulfonic acid groups, and 1.1 milliequivalents per gram ofdry resin of carboxylic acid groups.

This cation exchange membrane, which has an effective area of 100 dm²,is used to divide an electrolytic cell into a cathode chamber and ananode chamber. Fifty units of such electrolytic cell are arranged inseries so that the respective adjacent electrodes form a bipolar systemcomprising 50 electrolytic cells.

Using the thus prepared electrolytic cell assembly, electrolysis isconducted by charging 305 g/l of an aqueous sodium chloride solution toeach cell through the inlet of the anode chamber, and an aqueous sodiumhydroxide solution is recycled while being controlled at a concentrationof 35.5% by adding water to the outlet of the cathode chamber. Theelectrolysis is carried out while applying a current of 5,000 amperes tothe chambers in series.

In this case, the amount of the solution charged to the anode chamber iscontrolled to 11.515 kl/hr, water is added to the outlet of the cathodechamber, and the aqueous sodium hydroxide solution at the outlet of thecathode chamber is recycled. The current efficiency of the sodiumhydroxide recovered from the outlet of the cathode chamber is 95.8%.

COMPARISON EXAMPLE 1

A copolymer of perfluoro[2-(2-fluorosulfonylethoxy)propylvinylether]with tetrafluoroethylene is molded into a membrane 0.12 mm in thickness,which is then hydrolyzed to prepare a cation exchange membranecontaining 0.90 milliequivalent per gram of dry resin of sulfonic acidgroups.

This membrane is utilized in the same manner as in Example 1, but thecurrent efficiency while producing sodium hydroxide of 35.1%concentration is only 55.7%, and the amount of NaCl in the NaOH is 2,000p.p.m. Further, the specific electric conductivity of the membrane is11.3 mmho/cm as measured in a 0.1N aqueous NaOH solution at 25° C.

The specific electric conductivity of the membrane is measured in thefollowing manner.

The membrane is completely brought into the --SO₃ Na form and thenequilibrated by dipping at normal temperature for 10 hours in a 0.1Naqueous NaOH solution which is supplied continuously. Subsequently, theelectric resistivity of the membrane is measured in the solution byapplying an alternating current of 1,000 cycles, while maintaining thesolution at 25° C., and the specific electric conductivity is calculatedfrom the thickness and the effective area of the membrane.

COMPARISON EXAMPLE 2

The same copolymer as in Comparison Example 1 is molded into a membrane0.12 mm in thickness, and then hydrolyzed to prepare a cation exchangemembrane containing 0.65 milliequivalent per gram of dry resin ofsulfonic acid groups.

Using this membrane, electrolysis is conducted in the same manner as inExample 1, but the current efficiency while producing sodium hydroxideof 35.1% concentration is only 73%. The specific electric conductivityof the membrane is 4.5 mmho/cm as measured in a 0.1N aqueous NaOHsolution at 25° C.

EXAMPLE 2

The membrane of Comparison Example 1 is impregnated with methylperfluoro-5-oxa-6-heptenoate, which is then polymerized and hydrolyzedto prepare a cation exchange membrane having an exchange capacity, interms of sulfonic acid groups, of 0.77 milliequivalent per gram of dryresin, and an exchange capacity, in terms of carboxylic acid groups, of0.42 milliequivalent per gram of dry resin.

Using this cation exchange membrane, electrolysis is conducted in thesame manner as in Example 1. The current efficiency for producing sodiumhydroxide of 35.0% concentration is 96.2%. The amount of NaCl in theNaOH is only 150 p.p.m. Further, the specific electric conductivity ofthe membrane is 13.2 mmho/cm, and the cell voltage does not differ fromthat in Comparison Example 1.

EXAMPLE 3

A 2,3-dichloro-perfluorobutane solution of a ternary copolymer of CF₂═CFO(CF₂)₄ COOCH₃, CF₂ ═CFOCF₃ and tetrafluoroethylene is coated on oneside of the membrane of Comparison Example 1. After evaporating thesolvent, the membrane is hot-pressed and then hydrolyzed to prepare acation exchange membrane having a coating of 0.01 mm in thickness. Thethus prepared cation exchange membrane contains 0.83 milliequivalent pergram of dry resin of sulfonic acid groups and 0.05 milliequivalent pergram of dry resin of carboxylic acid groups.

Using this membrane, electrolysis is conducted in the same manner as inExample 1, while facing the coated side of the membrane to the cathode.The current efficiency for producing sodium hydroxide of 35.5%concentration is 97.1%.

EXAMPLE 4

A ternary copolymer comprisingperfluoro[2-(2-fluorosulfonylethoxy)-propylvinyl ether],tetrafluoroethylene and perfluoro-6-oxa-7-octenoyl fluoride is moldedinto a membrane of 0.12 mm in thickness, which is then hydrolyzed toprepare a cation exchange membrane containing 0.43 milliequivalent pergram of dry resin of sulfonic acid groups and 0.70 milliequivalent pergram of dry resin of carboxylic acid groups.

Using 50 sheets of this cation exchange membrane which has an effectivearea of 100 dm², electrolysis is conducted in the same manner and by useof the same apparatus as in Example 1, while applying a current of 5,000amperes to the 50 electrolytic cell units in series. The currentefficiency for producing sodium hydroxide of 35.6% concentration is98.8%, and the specific electric conductivity of the membrane is 9.0mmho/cm.

EXAMPLE 5

A quaternary copolymer comprisingperfluoro[2-(2-fluorosulfonylethoxy)-propylvinyl ether],tetrafluoroethylene, perfluoro-5-oxa-6-heptenoyl fluoride andperfluoropropyl perfluorovinyl ether is molded into a membrane 0.12 mmin thickness. After reinforcing with a Teflon fiber, the membrane ishydrolyzed to prepare a cation exchange membrane containing 0.84milliequivalent per gram of dry resin of sulfonic acid groups and 1.20milliequivalents per gram of dry resin of carboxylic acid groups.

Using this cation exchange membrane, electrolysis is conducted in thesame manner as in Example 1. The current efficiency for producing sodiumhydroxide of 36.0% concentration is 98.4%.

EXAMPLE 6

A cation exchange membrane is prepared by molding a ternary polymercomprising perfluoro[2-(2-fluorosulfonylethoxy)propylvinyl ether],tetrafluoroethylene and methyl perfluoro-6-oxa-7-octenoate into amembrane reinforced with a reticular material composed of Teflon,followed by hydrolysis.

This cation exchange membrane has 0.71 milliequivalent per gram of dryresin of sulfonic acid groups and 1.5 milliequivalents per gram of dryresin of carboxylic acid groups.

Using 50 sheets of this cation exchange membrane which has an effectivearea of 100 dm², electrolysis is conducted in the same manner and by useof the same electrolytic cell assembly as in Example 1, except that 305g/l of the aqueous sodium chloride solution is recycled in the anodechamber at a rate of 12.820 kl/hr, and water is continuously poured tothe exit solution of the cathode chamber so that the concentration ofsodium hydroxide in said exit solution is maintained at 31.1%. Theamount of the water is controlled to 767.65 kg/hr, and the electrolysisis carried out while applying a current of 5,000 amperes to the 50electrolytic cell units in series. The amount of chlorine generated inthe anode chamber is 311.2 kg/hr, the amount of 31.1% sodium hydroxidesolution recovered from the cathode chamber is 1,127.4 kg/hr, and theamount of hydrogen recovered from the cathode chamber is 9,325 g/hr. Thecurrent efficiency is 94%.

What is claimed is:
 1. A process for the electrolysis of an aqueoussodium chloride solution which comprises passing an electric currentthrough said solution in an electrolytic cell separated into an anodechamber and a cathode chamber by a cation exchange membrane consistingessentially of perfluorocarbon polymer having pendant carboxylic acidand sulfonic acid groups, said membrane having an ion exchange capacityof sulfonic and carboxylic acid groups of from 0.5 to 4.0milliequivalents per gram of dry resin, the ion exchange capacity of thecarboxylic acid groups being from 0.05 to 1.5 milliequivalents per gramof dry resin.
 2. The process of claim 1, wherein the perfluorocarbonpolymer having pendant carboxylic acid groups is present on the surfaceof the membrane.
 3. The process of claim 1, wherein a perfluorocarbonpolymer having pendant carboxylic acid groups is present on one surfaceof the membrane.
 4. The process of claim 1, wherein a perfluorocarbonpolymer having pendant carboxylic acid groups is present, together witha perfluorocarbon polymer having pendant sulfonic acid groups, on onesurface of the membrane.
 5. The process of claim 4, wherein aperfluorocarbon polymer having pendant sulfonic acid groups is presenton another surface of the membrane.
 6. The process of claim 1, whereinthe membrane in the sodium salt form has a water content of from 5 to50% by weight.
 7. The process of claim 1, wherein said membranecomprises a physical combination of perfluorocarbon polymer havingpendant carboxylic acid groups with perfluorocarbon polymer havingpendant sulfonic acid groups.
 8. The process of claim 1, wherein thecation exchange membrane is fiber reinforced.
 9. The process of claim 1,wherein said perfluorocarbon polymer is a copolymer of at least one oftetrafluoroethylene and CF₂ ═CF--O--R_(f) wherein R_(f) is aperfluorinated alkyl group containing 1 to 3 carbon atoms withperfluorocarbon vinyl monomers containing carboxylic acid groups andsulfonic acid groups or functional groups which can be converted tocarboxylic acid or sulfonic acid groups.
 10. The process of claim 1,wherein said perfluorocarbon polymer is a copolymer of a perfluorocarbonvinyl monomer having the general formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

wherein n is an integer of 2 to 12, and X is CN, COF, COOH, COOR, COOMor CONR₂ R₃ where R is an alkyl group containing 1 to 10 carbon atoms,R₂ and R₃ are individually hydrogen or an alkyl group containing 1 to 10carbon atoms, and M is sodium, potassium or cesium; and aperfluorocarbon sulfonyl fluoride having the general formula:

    F--SO.sub.2 --CFR.sub.g --CF.sub.2 --O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms, Y is fluorine or a trifluoromethyl group, and m is aninteger of 1 to 3, with at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms, which copolymer is hydrolyzed, if necessary, to formsaid acid groups.
 11. The process of claim 1, wherein saidperfluorocarbon polymer is a copolymer of a perfluoroacrylic acid havingthe general formula:

    CF.sub.2 ═CF--COZ

wherein Z is fluorine, an alkoxy group containing 1 to 10 carbon atoms,amino or hydroxy; and a perfluorocarbon sulfonyl fluoride having thegeneral formula:

    F--SO.sub.2 --CFR.sub.g --CF.sub.2 --O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms, Y is fluorine or a trifluoromethyl group, and m is aninteger of 1 to 3, with at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms, which copolymer is hydrolyzed, if necessary, to formsaid acid groups.
 12. The process of claim 1, wherein said cationexchange membrane is prepared by impregnating or coating a membrane of acopolymer of (A) a perfluorovinyl ether having the general formula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein L is hydroxy, fluorine or OA, where A is a quaternary ammoniumradical; R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3, and (B) at least one of tetrafluoroethylene and CF₂═CFOR_(f) wherein R_(f) is a perfluorinated alkyl group containing 1 to3 carbon atoms, with a perfluorovinyl compound having pendant carboxylicacid groups or derivatives thereof, polymerizing said impregnated orcoated vinyl compound, and hydrolyzing, if necessary, to form said acidgroups.
 13. The process of claim 12, wherein said perfluorovinylcompound is at least one member selected from the group consisting ofcompounds having the formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

wherein n is an integer of 2 to 12, and X is CN, COF, COOH, COOR, COOMor CONR₂ R₃, where R is an alkyl group containing 1 to 10 carbon atoms,R₂ and R₃ are individually hydrogen or an alkyl group containing 1 to 10carbon atoms, and M is sodium, potassium or cesium, and compounds havingthe formula:

    CF.sub.2 ═CF--COZ

wherein Z is fluorine or an alkoxy group containing 1 to 10 carbonatoms.
 14. The process of claim 1, wherein said cation exchange membraneis prepared by impregnating or coating a membrane of a copolymer of (A)a perfluorovinyl ether having the general formula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein L is hydroxy, fluorine or OA, where A is a quaternary ammoniumradical; R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3, and (B) at least one of tetrafluoroethylene and CF₂═CFOR_(f) wherein R_(f) is a perfluorinated alkyl group containing 1 to3 carbon atoms, with a solution of a perfluorocarbon polymer havingpendant carboxylic acid groups or derivatives thereof, and hydrolyzing,if necessary, to form said acid groups.
 15. A process according to claim12, 13 or 14, wherein the impregnating or coating is conducted on onesurface of the membrane.
 16. The process of claim 3, wherein saidcarboxylic acid groups are contained predominantly on said one surfaceof the membrane and wherein the membrane is disposed in saidelectrolytic cell such that said surface having the pendant carboxylicacid groups faces the cathode side of the cell.
 17. A process accordingto claim 9, 10, 11, 12, 13 or 14, wherein the cation exchange membraneis fiber reinforced.
 18. The process of claim 1, wherein the thicknessof the membrane is 0.05 to 1.5 mm.
 19. The process of claim 1, whereinthe electrolysis is conducted at a temperature of 0° to 150° C. whilecharging an aqueous sodium chloride solution into the anode chamber andadding water or an aqueous dilute sodium hydroxide solution into thecathode chamber to adjust the concentration of sodium hydroxide to morethan 20%.
 20. The process of claim 1, wherein the membrane has an ionexchange capacity of sulfonic and carboxylic acid groups of from about0.88 to about 2.21 milliequivalents per gram of dry resin.
 21. Theprocess of claim 1, wherein the electrolysis is conducted with a currentefficiency of greater than 90% at a concentration of sodium hydroxide ofmore than 20%.
 22. A process for the electrolysis of an aqueous sodiumchloride solution with high current efficiency at high concentrations ofsodium hydroxide which comprises passing an electric current throughsaid solution in an electrolytic cell separated into an anode chamberand a cathode chamber by a cation exchange membrane consistingessentially of perfluorocarbon polymer having pendant carboxylic acidand sulfonic acid groups, said membrane having an ion exchange capacityof sulfonic and carboxylic acid groups of from 0.5 to 4.0milliequivalents per gram of dry resin, the ion exchange capacity of thecarboxylic acid groups being from 0.05 to 1.5 milliequivalents per gramof dry resin.
 23. The process of claim 22, wherein the electrolysis isconducted with a current efficiency of greater than 90% at aconcentration of sodium hydroxide of more than 20%.
 24. A process forthe electrolysis of an aqueous sodium chloride solution which comprisespassing an electric current through said solution in an electrolyticcell separated into an anode chamber and a cathode chamber by a cationexchange membrane at a temperature of 0° to 150° C. while charging anaqueous sodium chloride solution which has been purified to a calciumcontent of less than 1 p.p.m. into the anode chamber and adding water oran aqueous dilute sodium hydroxide solution into the cathode chamber toadjust the concentration of sodium hydroxide therein to more than 20%,said membrane consisting essentially of perfluorocarbon polymer havingpendant carboxylic acid and sulfonic acid groups, the ion exchangecapacity of sulfonic and carboxylic acid groups being from 0.5 to 4.0milliequivalents per gram of dry resin, the ion exchange capacity of thecarboxylic acid groups being from 0.05 to 1.5 milliequivalents per gramof dry resin.
 25. The process of claim 24, wherein the aqueous sodiumchloride solution charged into the anode chamber is purified by ionexchange.
 26. The process of claim 24, wherein the membrane has an ionexchange capacity of sulfonic and carboxylic acid groups of from about0.88 to about 2.21 milliequivalents per gram of dry resin.
 27. A cationexchange membrane used in the electrolysis of an aqueous sodium chloridesolution consisting essentially of perfluorocarbon polymer havingpendant carboxylic acid and sulfonic acid groups, said membrane havingan ion exchange capacity of sulfonic and carboxylic acid groups of from0.5 to 4.0 milliequivalents per gram of dry resin, the ion exchangecapacity of the carboxylic acid groups being from 0.05 to 1.5milliequivalents per gram of dry resin.
 28. A cation exchange membranein accordance with claim 27, wherein a perfluorocarbon polymer havingpendant carboxylic acid groups is present on the surface of themembrane.
 29. A cation exchange membrane in accordance with claim 27,wherein a perfluorocarbon polymer having pendant carboxylic acid groupsis present on one surface of the membrane.
 30. A cation exchangemembrane in accordance with claim 27, wherein a perfluorocarbon polymerhaving pendant carboxylic acid groups is present, together with aperfluorocarbon polymer having pendant sulfonic acid groups, on onesurface of the membrane.
 31. A cation exchange membrane in accordancewith claim 30, wherein a perfluorocarbon polymer having pendant sulfonicacid groups is present on another surface of the membrane.
 32. A cationexchange membrane in accordance with claim 27, which has a water contentin the sodium salt form of from 5 to 50% by weight.
 33. A cationexchange membrane in accordance with claim 27, which comprises aphysical combination of perfluorocarbon polymer having pendantcarboxylic acid groups with perfluorocarbon polymer having pendantsulfonic acid groups.
 34. A cation exchange membrane in accordance withclaim 27, which includes a fiber reinforcement.
 35. A cation exchangemembrane in accordance with claim 27, wherein said perfluorocarbonpolymer is a copolymer of at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms with perfluorocarbon vinyl monomers containingcarboxylic acid groups and sulfonic acid groups or functional groupswhich can be converted to carboxylic acid or sulfonic acid groups.
 36. Acation exchange membrane in accordance with claim 27, wherein saidperfluorocarbon polymer is a copolymer of a perfluorocarbon vinylmonomer having the general formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

wherein n is an integer of 2 to 12, and X is CN, COF, COOH, COOR, COOMor CONR₂ R₃, where R is an alkyl group containing 1 to 10 carbon atoms,R₂ and R₃ are individually hydrogen or an alkyl group containing 1 to 10carbon atoms, and M is sodium, potassium or cesium; and aperfluorocarbon sulfonyl fluoride having the general formula:

    F--SO.sub.2 --CFR.sub.g --CF.sub.2 --O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms, Y is fluorine or a trifluoromethyl group, and m is aninteger of 1 to 3, with at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms, which copolymer is hydrolyzed, if necessary, to formsaid acid groups.
 37. A cation exchange membrane in accordance withclaim 27, wherein said perfluorocarbon polymer is a copolymer of aperfluoroacrylic acid having the general formula:

    CF.sub.2 ═CF--COZ

wherein Z is fluorine, an alkoxy group containing 1 to 10 carbon atoms,amino or hydroxy; and a perfluorocarbon sulfonyl fluoride having thegeneral formula:

    F--SO.sub.2 --CFR.sub.g --CF.sub.2 --O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms, Y is fluorine or a trifluoromethyl group, and m is aninteger of 1 to 3, with at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms, which copolymer is hydrolyzed, if necessary, to formsaid acid groups.
 38. A cation exchange membrane in accordance withclaim 27, wherein said cation exchange membrane is prepared byimpregnating or coating a membrane of a copolymer of (A) aperfluorovinyl ether having the general formula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein L is hydroxy, fluorine or OA, where A is a quaternary ammoniumradical; R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3, and (B) at least one of tetrafluoroethylene and CF₂═CFOR_(f) wherein R_(f) is a perfluorinated alkyl group containing 1 to3 carbon atoms, with a perfluorovinyl compound having pendant carboxylicacid groups or derivatives thereof, polymerizing said impregnated orcoated vinyl compound, and hydrolyzing, if necessary, to form said acidgroups.
 39. A cation exchange membrane in accordance with claim 38,wherein said perfluorovinyl compound is at least one member selectedfrom the group consisting of compounds having the formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

wherein n is an integer of 2 to 12, and X is CN, COF, COOH, COOR, COOMor CONR₂ R₃, where R is an alkyl group containing 1 to 10 carbon atoms,R₂ and R₃ are individually hydrogen or an alkyl group containing 1 to 10carbon atoms, and M is sodium, potassium or cesium, and compounds havingthe formula:

    CF.sub.2 ═CF--COZ

wherein Z is fluorine or an alkoxy group containing 1 to 10 carbonatoms.
 40. A cation exchange membrane in accordance with claim 27,wherein said cation exchange membrane is prepared by impregnating orcoating a membrane of a copolymer of (A) a perfluorovinyl ether havingthe general formula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein L is hydroxy, fluorine or OA, where A is a quaternary ammoniumradical; R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3, and (B) at least one of tetrafluoroethylene and CF₂═CFOR_(f) wherein R_(f) is a perfluorinated alkyl group containing 1 to3 carbon atoms, with a solution of a perfluorocarbon polymer havingpendant carboxylic acid groups or derivatives thereof, and hydrolyzing,if necessary, to form said acid groups.
 41. A cation exchange membranein accordance with claim 38, 39 or 40, wherein the impregnating orcoating is conducted on one surface of the membrane.
 42. A cationexchange membrane in accordance with claim 27, wherein the thickness ofthe membrane is 0.05 to 1.5 mm.
 43. A cation exchange membrane inaccordance with claim 27, wherein the ion exchange capacity of sulfonicand carboxylic acid groups is from about 0.88 to about 2.21milliequivalents per gram of dry resin.
 44. A cation exchange membraneused in the electrolysis of an aqueous sodium chloride solutionconsisting essentially of perfluorocarbon polymer having pendantcarboxylic acid and sulfonic acid groups, said membrane having an ionexchange capacity of sulfonic and carboxylic acid groups of from 0.5 to4.0 milliequivalents per gram of dry resin, the ion exchange capacity ofthe carboxylic acid groups being from 0.05 to 1.5 milliequivalents pergram of dry resin, said membrane providing high current efficiency athigh concentrations of sodium hydroxide.
 45. A cation exchange membranein accordance with claim 44, wherein said membrane is capable ofproviding a current efficiency of greater than 90% at a concentration ofsodium hydroxide of more than 20%.
 46. An electrolytic cell comprisingan anode chamber and a cathode chamber separated by a cation exchangemembrane which is used for the production of aqueous sodium hydroxide inthe cathode chamber by electrolysis wherein an aqueous solution ofsodium chloride is charged into the anode chamber, said membraneconsisting essentially of perfluorocarbon polymer having pendantcarboxylic acid and sulfonic acid groups, said membrane having an ionexchange capacity of sulfonic and carboxylic acid groups of from 0.5 to4.0 milliequivalents per gram of dry resin, the ion exchange capacity ofthe carboxylic acid groups being from 0.05 to 1.5 milliequivalents pergram of dry resin.
 47. An electrolytic cell in accordance with claim 46,wherein a perfluorocarbon polymer having pendant carboxylic acid groupsis present on the surface of the membrane.
 48. An electrolytic cell inaccordance with claim 46, wherein a perfluorocarbon polymer havingpendant carboxylic acid groups is present on one surface of themembrane.
 49. An electrolytic cell in accordance with claim 46, whereina perfluorocarbon polymer having pendant carboxylic acid groups ispresent, together with a perfluorocarbon polymer having pendant sulfonicacid groups, on one surface of the membrane.
 50. An electrolytic cell inaccordance with claim 49, wherein a perfluorocarbon polymer havingpendant sulfonic acid groups is present on another surface of themembrane.
 51. An electrolytic cell in accordance with claim 46, whereinthe membrane in the sodium salt form has a water content of from 5 to50% by weight.
 52. An electrolytic cell in accordance with claim 46,wherein the membrane comprises a physical combination of perfluorocarbonpolymer having pendant carboxylic acid groups with perfluorocarbonpolymer having pendant sulfonic acid groups.
 53. An electrolytic cell inaccordance with claim 46, wherein the cation exchange membrane is fiberreinforced.
 54. An electrolytic cell in accordance with claim 46,wherein said perfluorocarbon polymer is a copolymer of at least one oftetrafluoroethylene and CF₂ ═CF--O--R_(f) wherein R_(f) is aperfluorinated alkyl group containing 1 to 3 carbon atoms withperfluorocarbon vinyl monomers containing carboxylic acid groups andsulfonic acid groups or functional groups which can be converted tocarboxylic acid or sulfonic acid groups.
 55. An electrolytic cell inaccordance with claim 46, wherein said perfluorocarbon polymer is acopolymer of a perfluorocarbon vinyl monomer having the general formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

wherein n is an integer of 2 to 12, and X is CN, COF, COOH, COOR, COOMor CONR₂ R₃ where R is an alkyl group containing 1 to 10 carbon atoms,R₂ and R₃ are individually hydrogen or an alkyl group containing 1 to 10carbon atoms, and M is sodium, potassium or cesium; and aperfluorocarbon sulfonyl fluoride having the general formula:

    F--SO.sub.2 --CFR.sub.g --CF.sub.2 --O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms, Y is fluorine or a trifluoromethyl group, and m is aninteger of 1 to 3, with at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms, which copolymer is hydrolyzed, if necessary, to formsaid acid groups.
 56. An electrolytic cell in accordance with claim 46,wherein said perfluorocarbon polymer is a copolymer of aperfluoroacrylic acid having the general formula:

    CF.sub.2 ═CF--COZ

wherein Z is fluorine, an alkoxy group containing 1 to 10 carbon atoms,amino or hydroxy; and a perfluorocarbon sulfonyl fluoride having thegeneral formula:

    F--SO.sub.2 --CFR.sub.g --CF.sub.2 --O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms, Y is fluorine or a trifluoromethyl group, and m is aninteger of 1 to 3, with at least one of tetrafluoroethylene and CF₂═CF--O--R_(f) wherein R_(f) is a perfluorinated alkyl group containing 1to 3 carbon atoms, and hydrolyzing, if necessary, to form said acidgroups.
 57. An electrolytic cell in accordance with claim 46, whereinsaid cation exchange membrane is prepared by impregnating or coating amembrane of a copolymer of (A) a perfluorovinyl ether having the generalformula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein L is hydroxy, fluorine or OA, where A is a quaternary ammoniumradical; R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3, and (B) at least one of tetrafluoroethylene and CF₂═CFOR_(f) wherein R_(f) is a perfluorinated alkyl group containing 1 to3 carbon atoms, with a perfluorovinyl compound having pendant carboxylicacid groups or derivatives thereof, polymerizing said impregnated orcoated vinyl compound, and hydrolyzing, if necessary, to form said acidgroups.
 58. An electrolytic cell in accordance with claim 57, whereinsaid perfluorovinyl compound is at least one member selected from thegroup consisting of compounds having the formula:

    CF.sub.2 ═CF--O--(CF.sub.2).sub.n --X

wherein n is an integer of 2 to 12, and X is CN, COF, COOH, COOR, COOMor CONR₂ R₃, where R is an alkyl group containing 1 to 10 carbon atoms,R₂ and R₃ are individually hydrogen or an alkyl group containing 1 to 10carbon atoms, and M is sodium, potassium or cesium, and compounds havingthe formula:

    CF.sub.2 ═CF--COZ

wherein Z is fluorine or an alkoxy group containing 1 to 10 carbonatoms.
 59. An electrolytic cell in accordance with claim 46, whereinsaid cation exchange membrane is prepared by impregnating or coating amembrane of a copolymer of (A) a perfluorovinyl ether having the generalformula:

    LSO.sub.2 CFR.sub.g CF.sub.2 O(CFYCF.sub.2 O).sub.m --CF═CF.sub.2

wherein L is hydroxy, fluorine or OA, where A is a quaternary ammoniumradical; R_(g) is fluorine or a perfluoroalkyl group having 1 to 10carbon atoms; Y is fluorine or a trifluoromethyl group; and m is aninteger of 1 to 3, and (B) at least one of tetrafluoroethylene and CF₂═CFOR_(f) wherein R_(f) is a perfluorinated alkyl group containing 1 to3 carbon atoms, with a solution of a perfluorocarbon polymer havingpendant carboxylic acid groups or derivatives thereof, and hydrolyzing,if necessary, to form said acid groups.
 60. An electrolytic cell inaccordance with claim 57, 58 or 59, wherein the impregnating or coatingis conducted on one surface of the membrane.
 61. An electrolytic cell inaccordance with claim 48, wherein said carboxylic acid groups arecontained predominantly on said one surface of the membrane and whereinthe membrane is disposed in said electrolytic cell such that saidsurface having the pendant carboxylic acid groups faces the cathode sideof the cell.
 62. An electrolytic cell in accordance with claim 46,wherein the thickness of the membrane is 0.05 to 1.5 mm.
 63. Anelectrolytic cell in accordance with claim 46, wherein the membrane hasan ion exchange capacity of sulfonic and carboxylic acid groups of fromabout 0.88 to about 2.21 milliequivalents per gram of dry resin.
 64. Anelectrolytic cell comprising an anode chamber and a cathode chamberseparated by a cation exchange membrane which is used for the productionof aqueous sodium hydroxide in the cathode chamber by electrolysiswherein an aqueous solution of sodium chloride is charged into the anodechamber, said membrane consisting essentially of perfluorocarbon polymerhaving pendant carboxylic acid and sulfonic acid groups, said membranehaving an ion exchange capacity of sulfonic and carboxylic acid groupsof from 0.5 to 4.0 milliequivalents per gram of dry resin, the ionexchange capacity of the carboxylic acid groups being from 0.05 to 1.5milliequivalents per gram of dry resin, said membrane providing highcurrent efficiency at high concentrations of sodium hydroxide.
 65. Anelectrolytic cell in accordance with claim 64, wherein said membrane iscapable of providing a current efficiency of greater than 90% at aconcentration of sodium hydroxide of more than 20%.